Intermolecular addition

ABSTRACT

HYDROCYL MAGNESIUM COMPOUNDS (RMGX, R2MG) REACT WITH POLYCYCLIC COMPOUNDS CONTAINING ONE OR MORE ETHENO BRIDGES (E.G, BICYCLO(2,2.1) HEPT-2-ENE, BICYCLO(2.2.1)HEPTA-2,5-DIENE) TO PRODUCE VARIOUS NOVE POLYCYCLIC ORGANOMAGNESIUM COMPOUNDS. THESE IN TURN CAN BE SUBJECTED TO VARIOUS REACTIONS TO PRODUCE OTHER PRODUCTS.

United States Patent Olfice 3,810,949 Patented May 14, 1974 US. Cl.260-665 G 51 Claims ABSTRACT OF THE DISCLOSURE Hydrocarbyl magnesiumcompounds (RMgX; R Mg) react with polycyclic compounds containing one ormore etheno bridges (e.g., bicyclo[2.2.IJhept-Z-ene; bicyclo-[2.2.1]hepta-2,5-diene) to produce various novel polycyclicorganornagnesium compounds. These in turn can be subjected to variousreactions to produce other products.

REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of my prior copending application Ser. No. 888,071,filed Dec. 24, 1969 now abandoned.

This invention relates to the preparation and reactions oforganomagnesium compounds. More particularly, it relates to theformation of novel organomagnesium compounds via intermolecular additionbetween certain polycyclic compounds and organomagnesium reactants andto new and useful reactions and products based on the use of these novelorganomagnesium compounds.

BACKGROUND In U.S. 3,161,689 Cooper and Finkbeiner disclose that olefinsof the formula R-CH=CH react with an alkyl Grignard reagent of theformula R'MgX in the presence of titanium or zirconium catalysts such asTiCl Where the concentration of titanium or zirconium catalyst is low,the reaction predominately goes in the direction of producing a newGrignard reagent derived from the olefin displacing the R group of thealkyl Grignard reagent. On the other hand, where the titanium orzirconium catalyst is in a higher concentration range, there isincreased tendency toward the formation of addition products of theformula R'RCHCH MgX. Also see Cooper and Pinkbeiner, J. Org. Chem. 27,1493 (1962); Finkbeiner and Cooper, J. Org. Chem. 27, 3395 (1962);Finkbeiner and Cooper, Am. Chem. Soc., Div. Petrol. Chem., Preprints 8(2), B71-B78 (1963).

Tarrant and Heyes, J. Org. Chem. 30, 1485 (1965) describe the reactionof polyfluoro olefins with allylic Grignard reagents. In general, goodyields of allylfiuoroethylenes are achieved. The authors suggest areaction mechanism involving addition between the allylic Grignardreagent and the polyfluoro olefin followed by elimination of magnesiumdihalide. This reaction was successfully applied to such olefins astetrafiuoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene,unsym-dichlorodifiuoroethylene and hexafluoropropene. No reactionoccurred between allylmagnesium bromide and trifluoroethylene.

Eisch and Husk, J. Am. Chem. Soc., 87, 4194 (1965), report that ontreating allyldiphenylcarbinol in diethyl ether with two equivalents ofallylmagnesium bromide (25 C. for 36 hours) an addition reactionoccurred. Hydrolysis yielded the corresponding S-hexenyl carbinol.

o H y 6 1. 2CHz=CHCHzMgBr HO- CEICH=CH2 2. H2O 0H5 CaHuHo-hcmomcrnomorhom The authors indicated that further research wouldprobe the generality of this reaction by the use of other unsaturatedcarbinols and amines.

The addition of various fulvenes to certain Grignard reagents has beendescribed [Fuson and Porter, J. Am. Chem. Soc., 70, 895 (1948); Fuson,DeWald and Gaertner, J. Org. Chem., 16, 21. (1951); Fuson and Mumford,J. Org. Chem., 17, 255 (1952)]. The mechanism suggested for thesereactions involves participation of the conjugated exocyclic structureof the fulvenes.

Ziegler, Koster and Grimme indicate in US. 3,217,020 that ethylenereacts with magnesium alkyls to produce predominately polyethylene,there being no formation of longer chain magnesium alkyls throughaddition of the ethylene.

DESCRIPTION OF THE INVENTION This invention involves the discovery thathydrocarbyl magnesium compounds react with a variety of polycycliccompounds containing one or more etheno bridges to produce highermolecular weight organomagnesium compounds. In particular,intermolecular addition occurs between these reactants.

One embodiment of the invention is a process which comprises reacting ahydrocarbyl magnesium halide with a polycyclic compound having at leastone etheno bridge traversing the bridgehead carbon atoms of aninternally strained polycyclic molecule coreactive with the magnesiumcompound so that intermolecular addition occurs between said compounds.

The intermolecular addition reactions of this invention result in theformation of different types of end products, the course taken by thereaction being governed by the type of organomagnesium reactant andpolycyclic reactant utilized. Thus, this invention provides severalclasses of new compounds and several new reactions. This is illustratedby the exemplary reactions and products of this invention presentedbelow. For convenience, bicyclo[2.2.l] hepta-2,5-diene andbicyclo[2.2.1]hept-2-ene are utilized in these exemplifications asrepresentative polycyclic reactants, and Grignard reagents are shown asthe organomagnesium reactants. The invention is not limited to theiruse, however.

(a) Reaction of hydrocarbyl magnesium compounds (other than 2-alkenylmagnesium compounds) with polycyclic compounds containing two ethenobridges in the molecule to form a substituted nortricyclicorganomagnesium compound:

a mug: 5

Max

[R=alkyl, cycloalkyl, aryl, aralkyl, alkenyl (except 2-alkenyl),cycloalkenyl, etc.; X=Cl, Br, I].

(b) Reaction of 2-alkenyl magnesium compounds with polycyclic compoundscontaining two etheno bridges in the molecule (1:1 addition) to form atricyclo substituted methyl magnesium compound:

[R is defined above].

QBCH CRMMEX i it smu R crmu k macaw! m;

ans 301-12 01mm [R is defined above].

d. Reaction of Z-alkenyl manesium compounds with polycyclic compoundscontaining one etheno bridge in the molecule to form an alkenylsubstituted polycyclic organomagnesium compound:

It will be seen that reactions (a) through (d) above all involveintermolecular addition between the reactants. Further, in the case ofreaction (a) an intramolecular rearrangement occurs subsequent to theintermolecular addition whereas in reactions (b) and (c) intermolecularaddition is accompanied by the creation of a substituted fusedcyclobutane ring. In this connection, the products of reactions (b) and(c) are depicted in the exo form although it is to be understood thatthe products may exist in either the exo or endo form or may comprise amixture of both forms.

In another embodiment this invention furnishes new organomagnesiumhalides. These are exemplified by the following:

1. A nortricyclene characterized by having a hydrocarbyl substituent inthe 3 position and by having the 5 posi- 4 tion substituted by a --MgXgroup where X is Cl, Br, or I;

2. A tricycl0[4.2.l.0 ]n0n-7-ene characterized by having in the 3position a carbon-bonded substituent of the formula CH MgX where X isCl, Br, or I;

3. A tricyclo[4.2.1.0 ]nonane characterized by having in the 3 positiona carbon-bonded substituent of the formula CH MgX where X is Cl, Br, orI and by having the 7 or 8 position substituted by a MgX group where Xis Cl, Br, or I, the other said position being substituted by a2-alkenyl group;

4. A 3-(2-alkenyl)bicyclo[2.2.1]heptane characterized by having the 2position substituted by a MgX group Where X is Cl, Br or I; and

5. A tricyclo[5.2.1.0 ]dec-3-ene characterized by having the 8 or 9position substituted by a MgX group where X is Cl, Br, or I, the othersaid position being substituted by a 2-alkenyl group.

The preferred 2-alkenyl substitutent in the compounds of groups 3, 4,and 5 above is the allyl group.

Various polycyclic compounds may be used in practicing the process ofthis invention. As indicated by the above exemplary reactions, thepolycyclic reactant contains at least one etheno bridge in a polycyclicmolecule which may be considered as having an internal strain. Thus, thepolycyclic reactant includes such compounds as bicyclo [2.1 .0]pent-Z-ene;

bicyclo [3 2.0] hept-G-ene;

bicyclo 2.2. l hept-2-ene (2-norbornene) 1,3,3-trimethylbicyclo[2.2.1]hept-5-ene;

1,7,7-trimethylbicyclo[2.2.1]hept-2-ene (bornylene)2,2,5-trimethylbicyclo[2.2.1]hept-5-ene;

7,7-dimethylbicyclo[2.2.1]hept-2-ene apobornylene)3,3-dimethylbicyclo[2.2.1]hept-S-ene (camphenylene) 2,3-dimethylbicyclo2.2.1 [hept-Z-ene (santene) bicyclo 2.2.2 oct-2-ene;

bicyclo [3 .2.2. non-6-ene;

Z-methylbicyclo [2.2.2] oct-5-ene;

G-methylbicyclo 3 .2.2] non-6-ene;

bicyclo[8.2.2]tetradec-1l-ene;

tricyclo [3 220 non-6-ene;

3,3 -dimethyl-Z-methylenebicyclo[2.2.1]hept-5-ene (isocamphodiene);

S-ethylidenebicyclo[2.2.1]hept-2-ene;

cyclopentadiene dimer;

methylcyclopentadiene dimer;

butylcyclopentadiene dimer;

phenylcyclopentadiene dimer;

bicyclo[2.2.1]hepta-2,5-diene norbornadiene) 7-methylbicyclo [2.2. l]hepta-2, S-diene 1-methylbicyclo[2.2.1]hepta-2,5-diene;

7,7-dimethylbicyclo[2.2.1]hepta-2,5-diene;

1,7,7-trimethylbicyclo[2.2.1]hepta-2,5-diene;

l,4-diethylbicyclo[2.1.1]hepta-2,5-diene;

bicyclo [2.2.2] octa-2,5 ,7 -triene;

tricyclopentadiene;

and the like. Thus, among the categories of reactants of this type whichare coreactive with the organomagnesium reactant are the polycyclichydrocarbons containing at least one etheno bridge. These may berepresented by the formulas:

r r 3 :3 Rh. 1.. L

wherein, in the simplest cases, R and R are independently, hydrogen orlower alkyl groups; R is a divalent cyclic or acyclic hydrocarbonradical (i.e., a hydrocarbylene group) which may contain from 1 to about18 carbon atoms and which normally, but not necessarily, is from 1 to 3carbon atoms in length; and R is an alkylene or alkenylene group whichmay contain from 1 to about 18 carbon atoms and which normally is from 1to 3 carbon atoms in length. Of these, the compounds containing an Rbridge one carbon atom in length (i.e., methylene, monoalkyl substitutedmethylene and dialkyl substituted methylene) are preferred because oftheir high reactivity, ready availability and relatively low cost. Thesepreferred reactants may be represented by the formula:

wherein each of R R R and R is, individually, hydrogen or an alkyl groupand R is a divalent hydrocarbon radical from 1 to 3 carbon atoms inlength and containing from 1 to about carbon atoms.

The most preferred polycyclic reactants for use in this invention arebicyclo[2.2.l]hepta 2,5 diene; bicyclo [2.2.l]hepta-2,5-dienessubstituted with one or more lower alkyl groups or lower alkenyl groupsor both; bicyclo 2.2. l 1 hept-Z-ene; bicyclo [2.2. l hept-Z-enessubstituted with one or more lower alkyl groups or lower alkenyl groupsor both, cyclopentadiene dimer; and cyclopentadiene dimers substitutedwith one or more lower alkyl groups or lower alkenyl groups or both.

The organomagnesium reactants employed in accordance with this inventionmay be either Grignard reagents or diorganomagnesium compounds. Thusthis reactant has the formula where R is a hydrocarbyl group such asalkyl, cycloalkyl, aryl, aralkyl, alkenyl, cycloalkenyl, and the likeand R is either R or halogen. Mixtures of the Grignard reagent and itscorresponding diorganomagnesium compound may also be employed. Indeedsome investigators have suggested that a Grignard reagent involves anequilibrium between the organomagnesium halide and a mixture of themagnesium dihalide and diorganomagnesium. As between these two generalclasses of compounds the use of the Grignard reagents is preferred. Forone thing they are generally easier to prepare than the correspondingdiorganomagnesium compounds. Furthermore, by converting the initialGrignard reagent to the final Grignard reagent via the addition reactionof this invention one possesses a material susceptible to a wide varietyof uses.

Considering the nature of the hydrocarbon group(s) present in theorganomagnesium reactant, the 2-alkenyl compounds have been foundparticularly reactive and, as indicated by reactions (b) through (d)above, a variety of addition products can be achieved from their use.Although somewhat less reactive than the 2-alkenyl compounds, theremaining hydrocarbyl magnesium compounds lead to the formation of stillanother class of very interesting and novel addition products [notereaction (a) above]. The reactivities within a given class oforganomagnesium reactants will often vary. For example, primary alkylGrignard reagents will be found more reactive in the process than thecorresponding secondary alkyl Grignard reagents, presumably because ofsteric factors. The use of tertiary alkyl Grignard reagents is notrecommended as they react very slowly, if at all. The suitability of anygiven hydrocarbyl magnesium compound for use in the process of thisinvention can be readily ascertained by means of a simple trialexperiment.

Illustrative organomagnesium reactants are:

2-alkenyl compounds: allylmagnesium chloride, allylmagnesium bromide,allylmagnesium iodide, bis-allylmagnesium, methallyl magnesium chloride,methallyl magnesium bromide, methallyl magnesium iodine, bismethallylmagnesium, Z-butenyl magnesium chloride, 2- butenyl magnesium bromide,Z-butenyl magnesium iodide, bis-(2-butenyl)magnesium, 2-pentenylmagnesium chloride, Z-hexenyl magnesium bromide, 4-methyl-2-pentenylmagnesium bromide, cinnamyl magnesium bromide, and the like.

Other hydrocarbyl compounds: methylmagnesium bromide, ethylmagnesiumchloride, propylmagnesium bromide, isopropylmagnesium bromide,diisopropyl magnesium, butylmagnesium chloride, 2-octylmagnesium iodide,S-decyl magnesium bromide, cyclohexylmagnesium bromide, methylcyclohexylmagnesium chloride, bis-cyclohexyl magnesium, phenylmagnesium chloride,tolylmagnesium bromide, mesityl magnesium iodide, bis-cumenyl magnesium,benzylmagnesium chloride, 2-phenethyl magnesium bromide, p-methylbenzylmagnesium iodide, vinylmagnesium chloride, vinyl-magne-' sium bromide,propenylmagnesium bromide, cyclohexenyl magnesium bromide, and the like.

The most preferred 2-alkenyl magnesium compounds are allylmagnesiumchloride and allylmagnesium bromide. The most preferred of the otherhydrocarbyl magnesium compounds are the straight chain primary alkylmagnesium chlorides and bromides, especially where the alkyl groupscontain up to about 12 carbon atoms.

As a general rule the Grignard reagents will be subjected to theaddition reactions of this invention in a reaction medium composedpredominantly of an ether although, if desired, it is feasible toperform the reactions in a hydrocarbon medium. Thus, use may be made ofsuch ethers as dimethyl ether, diethyl ether, dibutyl ether,tetrahydrofuran, 2-methyl-tetrahydrofuran, 2,5-dimethyltetrahydrofuran,1,4-dioxane, the dimethyl ether of ethylene glycol, the dibutyl ether ofethylene glycol, the dimethyl ether of diethylene glycol, the diethylether of diethylene glycol, the dibutyl ether of diethylene glycol, andthe like. Pyridine, dimethyl sult'oxide, dimethyl formamide, hexamethylphosphoramide, or other strong Lewis base complexing solvents may alsobe suitable. Ordinarily the use of diethyl ether and dibutyl ether ispreferred.

If desired, the ether reaction media may be further diluted withinnocuous solvents such as aliphatic, cycloaliphatic or aromatichydrocarbons or the like.

The dihydrocarbyl magnesium reactants are usually produced and used in areaction medium composed predominately of a suitable paraffinic,cycloparafiinic or aromatic hydrocarbon (e.g., decane, dodecane, xylene,mesitylene and the like), although the use of an ether having a basicityof less than diethyl ether (e.g., diisopropyl ether, anisole, phenetole,diphenyl ether, phenyl isopropyl ether and the like) is feasible.

Reaction temperatures between about 50 and about 200 C. will usuallysuflice, temperatures falling in the range of about to about C. beingpreferred. Depending upon the reactants, solvent and temperature used,the pressure may range from atmospheric pressure up to about 100atmospheres or more. The usual precautions for Grignard reactions shouldbe o'bservede.g., the system should be kept essentially anhydrous andexposure to the atmosphere should be kept at a minimum.

This invention will become still further apparent from a considerationof the following illustrative examples.

7 EXAMPLE I Reaction between ethylmagnesium bromide and bicyclo[2.2.1]hepta-2,5-diene followed by hydrolysis A diethyl ether solutionof ethylmagnesium bromide (50 ml.; 52 mmoles) was placed in a75-milliliter bomb. Then 5.05 ml. (50 mmoles) ofbicyclo[2.2.l]hepta-2,5-diene (i.e., bicycloheptadiene or norbornadiene)was added. The bomb was sealed and heated for three hours at 125-140 C.A portion of the reaction mixture was hydrolyzed and analyzed by massspectrography. The hydrolyzed product was shown to have a molecularweight of 122 which corresponds to C H The hydrolysis product ofmolecular weight 122 was 3-ethylnortricyclene, the nortricyclicstructure being of known stability [Roberts, Trumble Jr., Bennett andArmstrong, J. Am. Chem. Soc. 72, 3116 (1950); Cowan and Krieghoff, J.Org. Chem. 32, 2639 (1967)].

Calls It was produced in an over-all yield of about 20 percent.

EXAMPLE 11 Reaction between ethylmagnesium bromide and bicyclo-[2.2.1]hepta-2,5-diene followed by hydrolysis A diethyl ether solutionof ethylmagnesium bromide (50 ml.; 78 mmoles) was placed in a75-milliliter bomb. Then 7.7 ml. (75 mmoles) of bicyclo[2.2.1]hepta-2,5-diene was added. The bomb was sealed and heated for forty hours at 140C. The product was hydrolyzed slowly over a period of one and one-halfhours with water in refluxing diethyl ether at 35 C. Hydrolysis wascompleted by adding excess aqueous ammonium chloride solution todissolve the magnesium salts. The ether solution was washed with waterand dried over magnesium sulfate. The ether was then removed atatmospheric pressure by heating in an oil bath at 50 C. The product wasthen vacuum distilled and the fraction boiling at 96 C. at 146-150 mm.Hg was isolated (2.23 grams). Analysis of this fraction by NMR, vpc andmass spectrography established that the compound was3-ethylnortricyclene having a purity of 94 percent. It was recovered ina yield of 24 percent.

EXAMPLE III Reaction between ethylmagnesium bromide and bicyclo[2.2.1]hepta-2,5-diene followed by oxidation and hydrolysis A diethylether solution of ethylmagnesium bromide (50 ml.; 78 mmoles) was placedin a 75-milliliter bomb and 7.7 ml. 75 mmoles) ofbicyclo[2.2.1]hepta-2,5-diene was added. The sealed bomb was heated for16 hours at 140 C. The reaction product was then oxidized by bubbling anexcess of pure oxygen through the solution while maintaining thetemperature at C. by means of an ice bath. Thereupon the product washydrolyzed with an aqueous ammonium chloride solution, diluted withdiethyl ether, and the ether layer was washed with water and dried overmagnesium sulfate. The ether solvent was stripped off by heating thesolution at 50 C. at atmospheric pressure. Vacuum distillation of theresidual material yielded 2.2 grams of close-boiling fraction, the majorportion of which boiled at 96 C. at 11 mm. Hg. Analysis of the productby means of vpc, infrared, and NMR showed it to consist of a mixture ofthree C alcohols in the proportions of 66 percent, 18 percent, andpercent; and that the mixture was composed of S-ethylbicyclo-[2.2.1]hept-2-en-6-ol and 3-ethylnortricyclen-5-ol as exo and endoisomers. These C alcohols were produced in an isolated yield of 21percent. Consequently in this reaction the organomagnesium product wasan equilibrium mixture of 3-ethylnortricyclen-5-yl magnesium bromide:

BrMg CZHS and 5-ethylbicyclo[2.2.1]hept-2-en-6-yl magnesium bromideEXAMPLE IV Reaction between isopropylmagnesium bromide andbicyclo[2.2.1]hepta-2,5-diene followed by hydrolysis MgBr EXAMPLE V 1:1reaction between allylmagnesium bromide and bicyclo-[2.2.1]hepta-2,5-diene followed by hydrolysis A 75-milliliter bomb wascharged with a diethyl ether solution of allylmagnesium bromide (50 ml.;46 mmoles) and 4.1 grams (4.5 ml.; 45 mmoles) of freshly distilledbicyclo[2.2.1]hepta- 2,5 -diene. The sealed bomb was heated in an oilbath at 150 C. for 3 hours, the contents of the bomb being agitatedseveral times during this period. The reaction mixture was treated withan aqueous solution of ammonium chloride and then the diethyl ethersolution was washed with water and dried over anhydrous magnesiumsulfate. After stripping off the ether solvent the product was vacuumdistilled (46 mm. Hg; pot temperature: 114117 C.; overhead temperature:8182 C.) and in this distillation 3.4 grams of distillate wererecovered. Analysis of the product by NMR (2 olefinic protons; 12aliphatic protons) and mass spectrography (molecular weight: 134)indicated the product to be 3-methyltricyclo- [4.2.1.0 ]non-7-ene:

It was produced in a yield of at least 55 percent.

Accordingly, the organomagnesium product of this reaction wastricyclo[4.2.1.0 ]non-7-en-3-yl-methylmagneslum bromide:

Further verification of the above structures was provided by subjectingthe hydrolysis product (C H to reduction in order to ascertainchemically whether it contained a cyclopropyl group or an olefinicdouble bond. In particular, 0.2 gram of a 5 percent platinum/asbestoshydrogenation catalyst was placed in 4 ml. of ethyl acetate. Then oneml. of the hydrolysis product (C H was added and the mixture treatedwith hydrogen at atmospheric pressure for about 16 hours at roomtemperature. By means of vpc and mass spectrographic analyses it wasestablished that reduction had occurred and that the hydrocarbon ofmolecular weight 134 had been converted during the reduction into a newproduct of molecular weight 136. Analysis by NMR of the reductionproduct confirmed the disappearance of the olefinic linkage and gave noevidence of cyclopropane protons. It was concluded therefore that thereduction product was 3- methyltricyclo[4.2.1.0 ]nonane:

EXAMPLE VI 1 :1 reaction between allylmagnesium bromide and bicycle-[2.2.1]hepta 2,5 diene followed by oxidation and hydrolysisAllylmagnesium bromide (50 mmoles) and bicyclo- [2.2.1]hepta-2,5-diene(50 mmoles) were reacted in diethyl ether in a sealed bomb by heatingfor 2.25 hours at 125 C. and one hour at 140 C. The reaction product wasthen oxidized at C. by passing gaseous oxygen through the product forabout 30 minutes. The resultant product was then hydrolyzed with waterfollowed by aqueous ammonium chloride solution and then water. Afterdrying the product over anhydrous magnesium sulfate, the diethyl ethersolvent was removed using a steam bath. The product was vacuum distilledand the fraction boiling at 95-101 C. at 2.5-3 mm. Hg was collected.This product, tricyclo[4.2.1.0 ]non-7-en-3-yl-methanol, was isolated ina 70 percent yield and its structure was supported by the results ofnuclear magnetic resonance studies. It may be depicted as follows:

CHaOH EXAMPLE VII 1:1 reaction between allylmagnesium bromide andbicyclo[2.2.1]hepta-2,5-diene followed by oxidation and hydrolysis Theprocedure of Example VI was repeated on a larger scale by reacting 195mmoles of allylmagnesium bromide in diethyl ether with 218 mmoles ofbicyclo[2.2.1]hepta- 2,5-diene at 125 C. for 3 hours. After theoxidation and hydrolysis, distillation gave tricyclo[4.2.1.0 ]non-7-en-3-yl-methanol (B.P. 97-99 C. at 1 mm. Hg) in 73 percent yield based onthe allylmagnesium bromide.

EXAMPLE VIII 1:1 reaction between allylmagnesium bromide andbicyclo[2.2.1]hepta-2,5-diene followed by oxidation bydrolysis andesterification A still larger quantity of tricyclo [4.2.1.0]non-7-ene-3- yl-methanol (i.e., B-methyloltricyclo [4.2.1.0 non-7-ene)10 was prepared by oxidizing and hydrolyzingthe product obtained byreaction of 260 mmoles of allylmagnesium bromide in diethyl ether with304 mmoles of bicyclo- [2.2.1]hepta-2,5-diene in a BOO-milliliter bombfor 3 hours at 122 C. with occasional shaking. The hydrolysis waseffected using dilute aqueous HCl followed by treatment with water,dilute aqueous sodium bicarbonate solution and then water. After dryingthe product, distillation gave the substituted methanol in 81 percentyield based on the allyl Grignard reagent employed. A portion of thisproduct was converted to the acetate ester by treating it with a mixtureof acetic anhydride, perchloric acid and ethyl acetate. Thisesterification yielded tricyclo- [4.2.l.0 ]non-7-en-3-yl-methyl acetate.Analysis by vpc showed that this ester was composed of two majorstereo-isomers in a ratio of approximately 5:1. Collectively the esterproduct can be represented by the formula:

n CH 0-CCH3 EXAMPLE IX 1:1 reaction between allylmagnesium bromide andbicyclo[2.2.l]hepta-2,5-diene followed by carbonation and hydrolysisTricyclo [4.2.1.0 ]non-7-en-3yl-methylmagnesium bromide was produced byreaction in diethyl ether between allylmagnesium bromide (130 moles) andbicyclo[2.2.1] hepta-2,5-diene (152 mmoles) at 125-l30 C. for 3 hours.The product was then carbonated by pouring it over a slurry of solidcarbon dioxide in diethyl ether at -78 C. Then the product washydrolyzed using dilute aqueous ammonium chloride followed by waterwashing. After drying, the solvent was removed from the product byvacuum distillation. The product which remained was then distilled usinga semi-micro distillation column and yielded a product fraction boilingat 129.5-" C. at 1.3 mm. Hg. Analyses by NMR and infrared showed theproduct was an olefinic acid and therefore the product wastricyclo[4.2.1.0 ]non-7-en-3-yl-acetic acid:

ii CH2 C OK It was recovered in a yield of 58 percent.

EXAMPLE X 2:1 reaction between allylmagnesium bromide andbicyclo[2.2.1]hepta-2,5-diene followed by hydrolysis A mixture of Ccompounds containing two C-Mg-Br bonds was produced by heating in asmall autoclave 20 mmoles of allylmagnesium bromide with 10 mmoles ofbicyclo[2.2.1]hepta-2,5-diene at 125' C. for 3 hours in a diethyl etherreaction medium. Hydrolysis of the reaction product liberated a mixtureof C hydrocarbons having four major components, i.e., the product wascomposed of positional and stereo-isomers. Thus, the reaction may bedepicted as follows:

.1. CH2 =CHCH MgBr CH MgBr Tricyclo[4.2.1.01non-7-en-3-y1-methylmagneslum bromide H MgBt 2 8? CH =CHCH HIM;

Brlig CHa= 2 7bromomagnesio-S-allyl-tricyclo [4.2.1.0 non3-ylmethylmagnesium bromide (at least two stereo-isomers)8-bromomagnesio-T-allyltrlcyelo [4.2.1.O non-3-yl methylmagnesiumbromide (at least two stereo-isomers) 8-allyl-3-methyltrlcyclo [4.2.1.0nonane (at least 'two stereo-isomers) 7-allyl-3-methyltrlcyclo [4.2.1.0nonane (at least two stereo-isomers) EXAMPLE XI Reaction betweenallylmagnesium bromide and bicyclo [2.2.1]hept-2-ene followed byhydrolysis or by oxidation and hydrolysis A diethyl ether solution ofallylmagnesium bromide (50 ml.; 50 mmoles) and bicyclo[2.2.l]hept-2-ene(4.7 grams; 50 mmoles) were heated in an autoclave at 135 C. for 3hours. -A small sample of the reaction product (1 ml.) was hydrolyzedand the liberated hydrocarbon product subjected to vpc and massspectrography analyses. It was shown that the hydrocarbon product had amolecular weight of 136 which corresponds to the empirical formula C HThe remainder of the reaction product was oxidized at 0 C. with oxygenand the resultant product subjected to hydrolysis using dilute aqueousammonium chloride solution. The ether solution from the hydrolysis waswashed with dilute HCl, water, aqueous sodium bicarbonate solution andwater, and then dried over magnesium sulfate. The dried product washeated on a steam bath to strip the diethyl ether and the residue wassubjected to vacuum distillation which yielded 3.9 grams of a producthaving a boiling point of 100 C. at 3 12 mm. Hg. Analysis by NMR andinfrared indicated the product to be 3-allyl-bicyclo[2.2.1]heptan-2-ol:

CH CH=CH It was recovered in 52 percent yield. When this terminallyunsaturated secondary alcohol was passed through a 0.02" x 150' Carbowax20M capillary column, it was separated into almost equal amounts of theendo and exo stereo-isomers. The Grignard reagent produced in thisexperiment was 3-allylbicyclo[2.2.1]hept-2-yl-magnesium bromide:

EXAMPLE XII Reaction between allylmagnesium bromide and bicyclo-[2.2.1]hept-2ene followed by hydrolysis A -milliliter bomb was chargedwith 50 ml. of allylmagnesium bromide/diethyl ether solution (50 mmolesof the Grignard reagent) and 4.7 grams (50 mmoles) ofbicyclo[2.2.1]hept-2-ene. The sealed bomb was heated in an oil bath for3 hours at C. The reaction product was hydrolyzed, water washed, driedand distilled at reduced pressure. This gave a 52 percent 3ield of2-allylbicyclo[2.2.1]heptane (i.e., Z-allylnorbornane) which boiled at8485 C. at 45 mm. Hg. In US. 3,183,220, Dekking reports the boilingpoint of this compound as 62-63 C. at 13 mm. Hg. Infrared and NMRanalyses of the product produced in this run were consistent with itsassigned structure.

EXAMPLE XIII Competitive reaction of bicyclo[2.2.l]hepta-2,S-diene andbicyclo[2.2.1]hept-2-ene with allylmagnesium bromide followed byhydrolysis A IO-milliliter bomb was charged with a diethyl ethersolution of allylmagnesium bromide (5 ml.; 5 mmoles), 5 mmoles ofbicyclo[2.2.1]hepta-2,5-diene and 5 mmoles of bicyclo[2.2.l]hept-2-ene.The bomb was sealed and heated for 3 hours at 125 C. in an oil bath. Theproduct was hydrolyzed, water washed, and dried, and then subjected tovpc analysis. It was found that the molar ratio between the3-methyltricyclo[4.2.1.0 non-7-ene and the 2-allylbicyclo[2.2.l]heptanewas 2.36:1 which indicates that the bicyclo[2.2.l]hepta-2,5-diene wasabout twice as reactive to the allyl Grignard reagent as was the bicyclo[2.2.1]hept2-ene.

EXAMPLE XIV Reaction between allylmagnesium bromide and cyclopentadienedimer followed by hydrolysis Allylmagnesium bromide 50 moles) andcyclopentadiene dimer (50 mmoles) were reacted in ether in a sealed bombat 125 C. for 3 hours. Hydrolysis of the 8-allyltricyclo [5.2.1.0dec-3-en-9-yl-magnesium bromide 9-allyltr'icyc1o[5.2.1.0]dec-3-en-8-yLmagnesium bromide CH =CHCH= Brl lg S-allyltrlcyclo[5.2.1.0dec-3-ene 9-ally1trlcyclo [5.2.1.O dec-3-ene From the above examples itwill be clear that there are various uses to which the organomagnesiumproducts of this invention may be put. Some of these novel uses areconsidered below.

A. Reactions of nortricyclic magnesium compounds (i) Preparation oftricyclenes having a hydrocarbyl substituent in the 3 position:

3 MgX hydrolysis This synthesis is accomplished by hydrolyzing a 3-hydrocarbyl nortricyclic magnesium compound which, in turn, may beprepared in accordance with this invention via reaction (a), supra. Toeffect this hydrolysis use may be made of water, dilute mineral acids,aqueous bases, aqueous ammonium chloride solutions, or the like. Thetemperature of the hydrolysis reaction is generally kept in the range offrom about to about 35 C.

Examples of compounds which may be produced in this manner includeB-methylnortricyclene; 3-propylnortricyclene; 3-octylnortr-icyclene;3-dodecylnortricyclene; 3-vinylnortricyclene; 3-benzylnortricyclene;S-phenylnortricyclene; 3,7-dirnethylnortricyclene;3-cyclohexyl-l-methylnortricyclene; S-butyl-1,2-dimethylnortricyclene;3-phenethyl-7,7-dimethylnortricyc1ene and the like.

(ii) Preparation of tricyclenes having a hydrocarbyl substituent in the3 position and a carboxyl group in the 5 position:

R e. carbonation R ligX b. hydrolysis reduced to form the correspondingaldehyde or it may be reduced further to produce the correspondingalcohol. If desired, the free acid may be converted into a metallic saltby treatment with an appropriate metallic oxide or hydroxide. Similarlythe free acid may be esterified by interaction with a suitablemonohydric or polyhydric alcohol, usually in the presence of aconventional esterification catalyst.

Examples of the compounds which may be produced in this manner are3-butylnortricyclen-S-yl-carboxylate;3-hexylnortricylen-5-yl-carboxylate;; 3-heptylnortricyclen-5-yl-carboxy1ate; 3-p-tolylnortricyclen-5-yl-carboxylate;3-cyclohex-3-enylnortricyclen-S-yI-carboxylate;3-butyl-l,4-dimethylnortricyclen-S-yl-carboxylate;1-methyl-3-(4-methylcyclohexyl)nortricyclen-S -yl-carboxylate;

the methyl, butyl, octyl and lauryl esters of each of these acids; thelithium, sodium, potassium, magnesium, calcium, zinc and aluminum saltsof each of these acids; and the alcohols and aldehydes from each ofthese acids.

(iii) Preparation of tricyclenes having a hydrocarbyl substituent in the3 position and a hydroxyl group in the 5 position:

In conducting this synthesis reaction a S-hydrocarbyl nortricyclicmagnesium compound is treated with oxygen or air under suitabletemperature and pressure conditions and the resultant intermediate isthen hydrolyzed as described in Section A(i) above. The reaction ispreferably conducted at temperatures in the range of about -40 to about65 C. using pressures ranging from about to about 1000 millimeters ofHg.

The cyclic alcohol in turn may be converted into other useful endproducts. Thus, for example, the nortricyclic alcohol may be esterifiedby treatment under esterification conditions with an organic acid orsuitable derivative thereof such as an acid anhydride or acid halide.Similarly, treatment of the cyclic alcohol with an active metal such assodium or potassium leads to the formation of the correspondingalcoholate salt. Reaction of the alcohol or its alkali metal salt withinorganic and organic phosphorus compounds (e.g., PCI POCl 'PSCl RPCl-(RO) POCl R an. oxidation Mgx '0. hydrolysis 3-methylnortricyclen-5'ol;3-ethylnortricyclen-5-o1; 3-isopropylnortricyclen-5-ol;3-butyl-7,7-dimethylnortricyclen-S-ol; 3 -(4-penteny1)nortricyclen-S-ol;1,4-dimethy1-3-octylnortricyclen-5-ol;

the acetyl, hexanoyl and decanoyl esters of each of these alcohols; thesodium and potassium salts of each of these alcohols; and the phosphite,phosphate and thiophosphate esters of each of these alcohols.

B. Reactions of tricyclo substituted methylmagnesium compounds (i)Preparation of 3-methyltricycloalkenes:

Ch t-15X hydrolyegs This reaction involves hydrolyzing atricyclo[4.2.l.0 non-7-en-3-yl-methylmagnesium halide which, in turn, isformed via reaction (b), supra.

The conditions used in this hydrolysis reaction are comparable to thosediscussed under Section A(i) above.

Typical products which may be produced in this manner include 3,4-dimethyltricyclo [4.2. 1. ]non-7-ene; 3,3-dimethyltricyclo [4.2. 1 .0non-7-ene;

3 ,9,9-trimethyltricyclo [4.2. 1 .0 non-7-ene;1,3,9,9-tetramethyltricyclo [4.2. l .0 non-7-ene;3-methyl-4-hexyltricyclo [4.2.1.0 non-7-ene;

and the like.

(ii) Preparation of 3-carboxymethyltricycloalkenes:

CligMgX a. carbonation b. hydrolysis i v F The reaction conditions usedin these carbonation and hydrolysis steps are comparable to thosedescribed in Section (A(ii) above. The resulting acids may beesterified,

reduced, or converted into metallic salts.

Compounds producible in this manner include 3-methyltricyclo [4.2.1.0non-7-en-3-yl-acetic acid; 4-n1ethyltricyclo[4.2.1.0]non-7-en-3-yl-acetic acid; 3,4-dimethyltricyclo [4.2. 1 .0 non-7-en-3-yl-acetic acid; 9,9-dimethyltricyclo[4.2.1.0 ]non-7-en-3-yl-aceticacid; 7,8-diethyltricyclo[4.2.l.0 ]non-7-en-3-yl-acetic acid;7-hexyltricyclo [4.2. 1 .0 non-7-en-3 -yl-acetic acid;

the aldehydes corresponding to each of these acids; the methyl, ethyl,butyl and phenethyl esters of each of these acids; and the lithium,sodium, potassium, calcium, barium and magnesium salts of each of theseacids.

(iii) Preparation of 3-methyloltricycloalkenes:

Cll llgX 8.. oxidation h. hydrolysis Cli COOH not; i

The conditions used in this synthesis reaction are comparable to thosedescribed in Section A(iii) above. The alcohols so formed may beesterified or converted into alcoholate salts.

Typical compounds which may be produced by means of this reactioninclude 3-methyltricyclo[4.2.1.0 non-7-en-3-yl-methan0l;4-methyltricyclo [4.2.1 .0 non-7-en-3yl-methanol; 4-ethyltricyclo[4.2.1.0 ]non-7-en-3-yl-methanol; 7-pentyltricyclo[4.2. 1.0non-7-en-3-yl-methanol; 9,9-dimethyltricyclo[4.2.1.0]non-7-en-3-yl-methanol; 3,7 -dimethyltricyclo [4.2.1.0]non-7-en-3-yl-methanol;

the acetyl, propionyl and heptanoyl esters of each of these :alcohols;the phosphite, phosphate and thiophosphate esters of each of thesealcohols; and the lithium, sodium and potassium salts of each of thesealcohols.

(3. Reactions of tricyclo substituted methylmagnesium compounds in whichthe Ring structure is directly bonded to a second magnesium atom (i)Preparation of 3-methyltricycloalkanes substituted in the ring by a2-alkenyl group:

CH MgX Y hydrolysis (Y or Z is 2-alkenyl, the other is MgX; W or V is 2-alkenyl, the other is H.)

In this synthesis the tricyclo di-Grignard reagent carrying a 2-alkenylgroup on the ring is subjected to hydrolysis utilizing the condimnsgiven in Section A(i) above. These di-Grignard reagents, in turn, areprepared according to this invention via reaction (c), supra.

Some of the compounds which may be prepared by means of this reactionare 7-methallyl-3-methyltricyclo[4.2.1.0 ]nonane;8-methallyl-3-methyltricyclo[4.2.1.0 nonane 7-crotonyl-3-methyltricyclo[4.2.1.0 nonane; 8-crotonyl-3-methyltricyclo [4.2. 1 11 nonane;7-pent-2-enyl-3-methyltricyclo [4.2. 1 .0 nonane; 8-pent-2-enyl-3-methyltricyclo [4.2. 1 .0 nonane;7-allyl-3,9,9-trimethyltricyclo[4.2.1.0 nonane; 8-ally1-3,9,9-trimethyltricyclo [4.2.1 .0 nonane;

and the like.

(ii) Preparation of 3-carboxymethyltricycloalkanes substituted in thering by a 2-alkenyl group and a carboxyl group:

Haw CH COUZ-K Y a. carbonation l I 2 to. hydrolysis U F (Y or Z is2-alkenyl, the other is MgX; T or U is 2- alkenyl, the other is COOH) Inconducting this reaction the conditions described in Section A(ii) aboveare employed.

The resultant polycyclic dibasic acid may, in turn, be subjected tovarious reactions such as partial reduction to an aldehyde or completereduction to a diol. Similarly the compound may be esterified or it maybe converted into metallic salts.

Typical compounds which may be synthesized in this manner include theethyl, butyl, heptyl and dodecyl esters and half esters of each of theseacids; the lithium, sodium, potassium, magnesium, and aluminum salts ofeach of these acids, the aldehydes and the diols derived by reducingeach of these acids; and the like.

(iii) Preparation of 3-methyloltricycloalkanes substituted in the ringby a 2-alkeny1 group and a hydroxy group:

cu u x 1 a. oxidation I, i z b. hydrolysis 5 7 (Y or Z is Z-alkenyl, theother is MgX; P or S is 2-ialkenyl, the other is OH).

The oxidation and hydrolysis conditions used in this synthesis procedureare as described in Section A(iii) above. The tricyclic diol thusproduced may be converted into other compounds. For example, the diolsmay be esterified or converted into alcoholate salts.

Utilization of these synthesis procedures enables the preparation ofsuch compounds as 7-allyl-8-hydroxy-tricyclo[4.2.1.0 ]non-3-yl-methanol;

8-allyl-7-hydroxy-tricyclo[4.2.1.0 non-3-yl-methanol;

7 -allyl-8-hydroxy-9,9- dimethyltricyclo [4.2.1 .0 non-3-ylmethanol;

the propionyl, heptanoyl and benzoyl esters of each of these diols; thesodium and potassium salts of each of these diols; and the dialkyl anddiaryl phosphite, phosphate and thiophosphate esters of each of thesediols.

D. Reactions of alkenyl polycyclic organomagnesium compounds (i)Preparation of 2-alkenyl polycycloalkanes:

I. hydrolysis L L is 2-alkenyl.)

In etfecting this hydrolysis reaction use should be made of theconditions described in Section A(i) above. The organomagnesium reactantutilized in this reaction is made in accordance with this invention viareaction (d), supra.

IIllustrative compounds which may be produced in this manner include2-methallylbicyclo[2.2.l]heptane; 2-crotonyl-bicyclo [2.2.1 ]heptane;2-pent-2-eny1-bicyclo [2.2. l heptane;Z-allyl-l-methylbicyclo[2.2.1]heptane; 2-allyl-7,7-dimethyl-bicyclo[2.2.1]heptane; and the like.

(ii) Preparation of 2-alkenyl polycycloalkane carboxylates:

1, L imp: icons,

The conditions described in Section A(ii) above are (L is 2-a1kenyl.)

utilized for this reaction.

The resultant acid may be converted into other useful derivatives suchas esters, aldehydes, alcohols, metallic salts, and the like.

Some of the compounds which may be prepared in this manner include I.carbonation b. hydrolysis the methyl, ethyl, butyl and octyl esters ofeach of these acids; the lithium, sodium, potassium, calcium, magnesiumand zinc salts of each of these acids; and the aldehydes and alcoholsobtained by reducing each of these acids.

(iii) Preparation of 2-alkenyl polycycloalkanols:

(L is Z-alkenyl.)

For the conditions used in this reaction, see Section I. oxidation b.hydrolysis -A(iii) above.

The alcohols produced in this reaction sequence may be converted intoother useful products, e.g., by esterification, etc.

Some of the compounds which may be produced by means of this reactionare 3-allylbicyclo [2.2. 1 heptan-Z-ol;

3-methallylbicyclo[2.2.1]heptan-2-ol;

3-crotonylbicyclo[2.2.1]heptan-2-ol;

3-allyl-7,7-dimethylbicyclo [2.2. l 1 heptan-2-ol;

3-ally1-1-methylbicyclo [2.2.1 ]heptan-2-ol;

3-allyl-4-methylbicyclo 2.2. 1 heptan-Z-ol;

8-allyltricyclo [5.2.1.0 ]dec-2-en-9-ol;

9-allyltricyclo [5.2. l .0 dec-3-en-8-ol 8-allyl-4,5,1-0,IO-tetramethyltricyclo[5.2. LO Jdec-Zien-9-ol;

9-allyl-4,5,10 IO-tetramethyltricyclo [5.2. 1.0] doc-3- en-8-ol;

the acetyl, neohexanoyl and octanoyl esters of each of these alcohols;the phosphite, phosphate, and thiophos phate esters of each of thesealcohols; and the lithium, sodium, and potassium salts of each of thesealcohols.

For convenience the above exemplifications of various reactions andproducts of this invention have been discussed primarily in terms of useand formation of polycyclo Grignard reagents. It will be appreciatedthat the corresponding bis-hydrocarbyl magnesium compounds may be formedand utilized in the same general fashion.

It is also to be understood and appreciated that although various threedimensional molecular structures have been depicted in this descriptionof the invention, it is not intended that the invention be limited toany given geometric or stereo-isomer. The three dimensional formulashave been utilized simply as a convenient way of depicting the complexpolycyclic compounds involved in the practice of this invention.

It can readily be seen from the above description that various new anduseful compounds are produced according to this invention. For example,this invention provides nortricyclenes having a hydrocarbyl substituentin the 3 position, including those wherein the 5 position is substitutedby a functional group such as, for example, a --MgX group and Where X isCl, Br, or I.

Another class of compounds provided by this invention comprises thetricyclo[4.2.'l.0 ]non-7-enes having a carbon-bonded substituent in the3 position. Of these compounds, those in which the substituent is afunctional group are of the widest utilities. Exemplary of suchfunctional groups are the CH MgX group where X is Cl, Br, or I; themethylol group; esterified methylol groups; the carboxymethyl group andthe like.

Still another class of compounds provided by this invention is made upof tricyclo[4.2.l.0 ]nonanes having a carbon-bonded substituent in the 3position, including those where the substituent is a functional group.Included within this class are compounds wherein the functionalsubstituent in the 3 position is a --CH MgX group where X is Cl, Br, orI and wherein the 7 or 8 position is substituted by a -MgX group where Xis Cl, Br, or I, the other said position being substituted by a2-alkenyl group.

A further class of novel compounds provided by this invention iscomposed of 3-(2-alkenyl)bicyclo[2.2.1]heptanes having a functionalsubstituent in the 2 position, e.g., a -MgX group or a hydroxyl group.

Still other novel compounds are included within the foregoingdisclosure.

The novel compounds of this: invention are of considerable utility. Asindicated above, the novel organomagnesium compounds of this inventionare especially adapted for use as chemical intermediates in thesynthesis of other useful chemicals.

ized with ethylene in accordance with known Ziegler/ Natta typetechnology in order to form a variety of polymers of differing physicalproperties. Various compounds of this invention may also find use in themanufacture of synthetic detergents (e.g., for dishwashing and laundryusage) and in the manufacture of lubricating oil additives. Some of thecompounds of this invention may be used directly as, or as intermediatesfor the manufacture of, flotation chemicals, germicides, insecticides,fungicides, insect repellants, Waterproofing agents, plasticizers, andemulsifying agents. In addition, the flammable compounds of thisinvention may be used as sources of heat, light, carbon dioxide andwater.

Other uses for the compounds of this invention will become evident tothose skilled in the art.

What is claimed is:

1. A process which comprises reacting a hydrocarbyl magnesium halidewith a polycyclic hydrocarbon compound having at least one etheno bridgetraversing the bridgehead carbon atoms of an internally strainedpolycyclic molecule coreactive with the magnesium compound so thatintermolecular addition occurs between said compounds.

2. The process of claim 1 wherein said magnesium compound is allylmagnesium bromide or allyl magnesium chloride.

3. The process of claim 1 wherein said magnesium compound is allylmagnesium bromide or allyl magnesium chloride and wherein saidpolycyclic compound is bicyclo [2.2.l]hepta-2,5-diene.

4. The process of claim 1 wherein said magnesium compound is allylmagnesium bromide or allyl magnesium chloride and wherein saidpolycyclic compound is bicyclo [2.2.1]hepta-2,5-diene, said compoundsbeing reacted in relative proportions such that intermolecular additionoccurs with essentially only one of the etheno bridges of said diene.

5. A process which comprises reacting a hydrocarbyl magnesium halidecompound with a polycyclic compound containing at least one ethenobridge coreactive with the magnesium compound to effect intermolecularaddition between said compounds, said polycyclic compound having theformula wherein R and R are hydrogen or lower alkyl groups, R is adivalent hydrocarbon group from 1 to 3 carbon atoms in length andcontaining from 1 to about 18 carbon atoms and R is an alkylene oralkenylene group from 1 to 3 carbon atoms in length and containing from1 to about 18 carbon atoms.

6. The process of claim 5 wherein said magnesium compound is an alkylGrignard reagent and the reaction is conducted in an ether reactionmedium.

7. The process of claim 5 wherein said magnesium compound is allylmagnesium bromide or allyl magnesium chloride and the reaction isconducted in an ether reaction medium.

8. The process of claim 5 wherein said magnesium compound is a2-al'kenyl magnesium compound and the reaction is conducted in an etherreaction medium.

9. The process of claim 1 wherein said polycyclic compound isbicyclo[2.2.l]hepta 2,5 diene; bicyclo- [2.2.l]hepta-2,5-dienesubstituted with one or more lower alkyl groups or lower alkenyl groupsor both; bicyclo- [2.2.1]hcpt-2-ene; bicyclo[2.2.1]hept-2-enesubstituted with one or more lower alkyl groups or lower alkenyl groupsor both, cyclopentadiene dimer; or cyclopentadiene dimer substitutedwith one or more lower alkyl groups or lower alkenyl groups or both.

10. The process of claim 5 wherein said magnesium compound is allylmagnesium bromide or allyl magnesium chloride.

11. The process of claim 5 wherein said magnesium compound is a straightchain primary alkyl magnesium chloride or bromide in which the alkylgroup contains up to about 12 carbon atoms.

12. The process of claim 5 wherein said magnesium compound is an alkylGrignard reagent.

13. The process of claim 5 wherein said magnesium compound is a primaryalkyl Grignard reagent.

14. The process of claim 5 wherein said magnesium compound is asecondary alkyl Grignard reagent.

15. The process of claim 5 wherein the reaction is conducted in an etherreaction medium.

16. The process of claim 5 wherein said polycyclic compound has theformula:

wherein each of R R R and R is, individually, hydrogen or an alkyl groupand R is a divalent hydrocarbon radical from 1 to 3 carbon atoms inlength and containing from 1 to about 10 carbon atoms.

17. The process of claim 5 wherein said polycyclic compound is a bicyclo[2.2.1]hept-2-ene.

18. The process of claim 5 wherein said polycyclic compound is abicyclo[2.2.l]hepta-2,5-diene.

19. The process of claim 5 wherein said polycyclic compound is a dimerof cyclopentadiene or of an alkyl substituted cyclopentadiene.

.20. The process of claim 5 wherein said magnesium compound is a2-alkenyl magnesium halide and said polycyclic compound is abicyclo[2.2.l]hept-2-ene.

21. The process of claim 5 wherein said magnesium compound is a primaryalkyl magnesium halide or a secondary alkyl magnesium halide and saidpolycyclic compound is a bicyclo[2.2.1]hepta-2,5-diene.

22. The process of claim 5 wherein said magnesium compound is a2-a1kenyl magnesium halide and said polycyclic compound is abicyclo[2.2.1]hepta-2,5-diene.

23. The process of claim 5 wherein said magnesium compound is allylmagnesium bromide and said polycyclic compound isbicyclo[2.2.1]hept-2-ene and wherein the reaction is conducted indiethyl ether at an elevated temperature.

24. The process of claim 5 wherein said magnesium compound is allylmagnesium bromide and said polycyclic compound isbicyclo[2.2.1]hepta-2,5-diene and wherein said reaction is conducted indiethyl ether at an elevated temperature.

25. The process of claim 5 wherein said magnesium compound is allylmagnesium bromide and said polycyclic compound is cyclopentadiene dimerand wherein the reaction is conducted in diethyl ether at an elevatedtemperature.

26. The process of claim 5 wherein said magnesium compound is a loweralkyl Grignard reagent and said polycyclic compound isbicyclo[2.2.l]hepta-2,5-diene and wherein the reaction is conducted indiethyl ether at an elevated temperature.

27. The process of claim 5 wherein said magnesium compound is a2-alkenyl magnesium halide and said polycyclic compound is abicyclo[2.2.1]hepta-2,5-diene, said compounds being reacted in relativeproportions such that intermolecular addition occurs with essentiallyonly one of the etheno bridges of said diene.

28. The process of claim 5 wherein said magnesium compound is a2-alkenyl magnesium halide and said polycyclic compound is abicyclo[2.2.l]hepta-2,5-diene, said compounds being reacted in relativeproportions such that intermolecular addition occurs with essentiallyonly one of the etheno bridges of said diene; and wherein the reactionis conducted in an ether reaction medium at an elevated temperature.

29. The process of claim wherein said magnesium compound is a 2-alkenylmagnesium halide and said polycyclic compound is abicyclo[2.2.1]hepta-2,5-diene, said compounds being reacted in relativeproportions such that intermolecular addition occurs with essentiallyboth of the etheno bridges of said diene.

30. The process of claim 5 wherein said magnesium compound is aZ-alkenyl magnesium halide and said polycyclic compound is abicyclo[2.2.1]hepta-2,5-diene, said compounds being reacted in relativeproportions such that intermolecular addition occurs with essentiallyboth of the etheno bridges of said diene; and wherein the reaction isconducted in an ether reaction medium at an elevated temperature.

31. An organomagnesium halide selected from the group consisting of (a)a nortricyclene characterized by having a lower hydrocarbyl substituentin the 3 position and by having the 5 position substituted by a --MgXgroup where X is Cl, Br, or I, additional substitution in the molecule,if any, being limited to lower alkyl substitution;

(b) a tricyclo[4.2.1.0 ]non-7-ene characterized by having in the 3position a carbon-bonded substituent of the formula -CH MgX where X isCl, Br, or I, additional substitution in the molecule, if any, beinglimited to lower alkyl substitution;

(c) a tricyclo[4.2.1.0 nonane characterized by having the 3 position acarbon-bonded substituent of the formula CH MgX where X is Cl, Br, or Iand by having the 7 or 8 position substituted by a MgX group where X isCl, Br, or I, the other said position being substituted by a lower2-alkenyl group, additional substitution in the molecule, if any, beinglimited to lower alkyl substitution;

(d) a 3-(lower 2- alkenyl)bicyc1o[2.2.l]heptane characterized by havingthe 2 position substituted by a MgX group where X is Cl, Br, or 1,additional substitution in the molecule, if any, being limited to loweralkyl substitution; and

(e) a tricyclo[5.2.1.0 ]dec-3-ene characterized by having the 8 or 9position substituted by a MgX group where X is Cl, Br, or I, the othersaid position being substituted by a lower 2-alkenyl group, additionalsubstitution in the molecule, if any, being limited to lower alkylsubstitution.

32. A compound according to claim 31 wherein the organomagnesium halideis a nortricyclene as defined in (a) therein.

33. A compound according to claim 31 having the formula:

wherein R is a lower hydrocarbyl group and X is Cl, Br, or I.

34. A compound according to claim 31 wherein the hydrocanbyl group inthe 3 position is a primary alkyl group.

35. A compound according to claim 31, viz,S-ethylnortricyclen-S-yl-magnesium bromide.

36. A compound according to claim 31, viz,S-ethylnortricyclen-S-yl-magnesium bromide, in an equilibrium mixturewith 5-ethylbicyclo[2.2.l]hept-2-en-6-yl magnesium bromide.

37. A compound according to claim 31 wherein the organomagnesium halideis a tricyclo[4.2.l.0 ]non-7-ene as defined in (b) therein.

38. A compound according to claim 31 having the formula:

wherein R is hydrogen or a lower hydrocarbyl group and X is Cl, Br, orI.

39. A compound according to claim 31, viz, tricyclo [4.2.l.0 ]non-7-enehaving in the 3 position a carbonbonded substituent of the structurewhere X is Cl, Br, or I.

40. A compound according to claim 31, viz, tricyclo [4.2.1.0]non-7-en-3yl-methylmagnesium bromide.

41. A compound according to claim 31 wherein the organomagnesium halideis a tricyclo [4.2.1.0 ]nonane as defined in (c) therein.

42. A compound according to claim 41 wherein said 2-alkenyl group in the7 or 8 position is the allyl group.

43. A compound according to claim 41, viz,7-bromomagnesio-8-allyltricyclo[4.2.1.0 ]non 3 yl methylmagnesiumbromide.

44. A compound according to claim 41, viz,8-brornomagnesio-7-allyltricyclo[4.2.1.0 ]non 3 yl methylmagnesiumbromide.

45. A compound according to claim 31 wherein the organomagnesium halideis a 3-(2-alkenyl)bicyclo[2.2.1] heptane as defined in (d) therein.

46. A compound according to claim 45 wherein said 2-alkenyl group is theallyl group.

47. A compound according to claim 45, viz,3-allylbicyc1o[2.2.1]hept-2-yl-magnesium bromide.

48. A compound according to claim 31 wherein the organornagnesium halideis a tricyclo[5.2.1.0 ]dec-3-ene as defined in (e) therein.

49. A compound according to claim 48 wherein said 2-alkenyl group in the8 or 9 position is the allyl group.

50. A compound according to claim 48, viz, 8-ally1- tricycl0[5.2.1.0dec-3-en-9-yl-magnesium bromide.

51. A compound according to claim 48, viz, 9-allyltricyclo [5.2.1 .0dec-3-en-8-yl-magnesium bromide.

References Cited UNITED STATES PATENTS 3,418,369 12/1968 Kauer 260-665 G3,444,199 5/1969 Whitney 260-665 G DANIEL E. WYMAN, Primary Examiner A.P. DEMERS, Assistant Examiner U.S. Cl. X.R.

260-468 T, 488 R, 514 B, 617 R, 666 A, 666 R m g?" UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION Patent No. 3, 810, 9 9 Dated M y 97Inve i-( Lawrence H. Shepherd, Jr.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 3, line 25, "compound" should read compounds Column 4, line 57,[2.2.1[hept-2-ene" should read [2.2.1]hept-2-ene Column 5, line 27,"each of R should read each of R Column 9, line 74, "[4 2 l O shouldread [4.2.1.0 line 74, "non-7-ene-3-" should read non-T-en-B- --3 line75, "[4.2.l.O should read Column 10, line 55, "[4.2.1.o should read+.2.l.O line 37, "(130 moles) should read (130 mmoles) Column 11, line30, a portion of the righthand formula is illegible and should read Anu, Mm: v1.1.4 1|- by BrMg CH =CHCH Column 12, line 43, "SH-85C." shouldread --'8 l-.-84.5C.

Column 13, line 63, a portion of the right-hand formula is illegible andshould read COOH Page 1 of 2 Pages 53 3? UNITED S'IATES PATENT OFFICE 4CERTIFICATE OF CORRECTION Patent No. 5: 9 Dated May 197a Inventor(s)Lawrence H. Shepherd, Jr.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 14, line 49, e.g. P01 should read (e. g. PCl line 53, "0t" shouldread to Column 15, line 23, "(A( ii) should read A( ii) --3 line 50,"non-Y-en-ByL-methangl; should read non-7- en-5-yl-methanol;

Column 18, line 9, "dec-2-en-9-ol" should read dec-3-en-9-ol Signed andsealed this 1st day of April 1975.

(SEAL) int-test. c. MARSHALL DANN RUTH C. MASON Commissioner of PatentsAttesting Officer and Trademarks Page 2 of 2 Pages

